Using integrated noble gas and hydrocarbon geochemistry to constrain the source of hydrocarbon gases in shallow aquifers in the northern Appalachian Basin

Authors: DARRAH, Thomas1*, VENGOSH, Avner1, JACKSON, Robert1,2, WARNER, Nathaniel1, Walsh, T.3, and POREDA, Robert3 (1) Division of Earth and Ocean Sciences, Nicholas School of the Environment, Duke University, Durham, NC 27708, [email protected]; (2) Nicholas School of the Environment and Center on Global Change, Duke University, Box 90338, Durham, NC 27708; (3) Department of Earth & Environmental Sciences, University of Rochester, 227 Hutchison Hall, Rochester, NY 14627 *Corresponding author email: [email protected]

I. Abstract III. Geological Background IV. Dissolved Gas and Inorganic Tracers

Rising demands for domestic energy sources, mandates for cleaner burning fuels for The Appalachian Basin is an archetypal energy-producing foreland basin that has evolved in electricity generation, and the approach of peak global hydrocarbon production are driving the response to complex tectonic processes and climatic conditions since the Paleozoic (e.g., Faill, 1997). In transformation from coal to natural gas from unconventional energy resources. This transit has been the NAB, the Paleozoic sedimentary rocks were deposited during the Taconic and Acadian orogenies and aided by recent advances in horizontal drilling and hydraulic fracturing technologies, which have deformed in the subsequent Alleghanian orogeny (Ettensohn and Brett, 2002). Today the complex substantially increased the potential for the recovery of natural gas and oil from organic-rich black depositional and tectonic history of this area is subtly expressed within the northern section of Appalachian shales globally. Nonetheless, public and political enthusiasm and consent is tempered by various Plateau physiographic province as gently dipping strata (overall dip magnitudes of ~ 1-3 degrees) that are concerns regarding the environmental risks associated with shale gas development, specifically broadly folded due to salt cored detachment folds, and further deformed by layer parallel shortening, drinking-water quality (e.g. contamination from hydraulic fracturing fluids, production/flow back waters, reverse faults, and fracturing (e.g., Davis and Engelder, 1985; Engelder, 1979; Sak et al., 2012). and/or stray combustible gases). Thus, questions and concerns regarding the significance of elevated The oldest lithologies of interest in the study area consist of the interbedded limestones and levels of combustible gas in shallow aquifers has been at the forefront of these concerns. shales of the Middle Ordovician Trenton/Black River Group. These rocks, and the overlying organic-rich Utica shale, represent Taconic orogenic sediments (Milici and Witt, 1988). The lower most Silurian age Previously, Osborn et al 2011 identified 17-times higher concentrations of thermally strata contains the fine-grained Tuscarora Formation sandstones, while the Upper Silurian is characterized mature methane (CH4) and aliphatic hydrocarbons (e.g. ethane (C2H6)) in drinking water wells within by the transition from the Silurian Lockport Dolomite/McKenzie argillaceous limestone to the Bloomsburg 1km of shale gas development sites producing from the Marcellus Shale in northeastern Pennsylvania. red sandstone and evaporitic Salina Group (Straeten et al., 1994). The Salina Group consists of While these findings suggest a correlation between areas of shale gas development and elevated interbedded shales, dolomites, and salt deposits that act as the regional decollement for Alleghanian methane concentrations in shallow aquifers, others suggest that the presence of methane in shallow structures (Scanlin and Engelder, 2003). As a result, structural folds and faults above the decollement (i.e. groundwater aquifers is common, natural, and unrelated to shale gas development (e.g. Molofsky et Devonian and younger stratigraphic units) bear little resemblance in deformation style to those present n al, 2011). Indeed, examples of natural methane seeps are identified in the northern Appalachian Basin beneath the Salina Group (e.g., Scanlin and Engelder, 2003). (e.g. Salt Spring State Park, Montrose, PA) (Warner et al, 2012). The transition from Upper Silurian to Lower Devonian is comprised of the Upper Silurian Helderberg Group (layered dolomites and limestones) and Lower Devonian Oriskany Sandstone. At the The potential for elevated methane concentrations from both natural geological base of the Middle Devonian sits the Onondaga/Selinsgrove limestones, which lies directly beneath the migration and anthropogenic activities highlights the need to develop and validate advanced Middle Devonian aged Hamilton Group (Straeten et al., 2011). The Hamilton Group is an eastward to geochemical systematics (e.g. integrated noble gas and hydrocarbon molecular and isotope southeastward thickening wedge of marine sediments that includes the organic- and siliciclastic-rich, geochemistry) capable of evaluating the source, timing, and migration history of hydrocarbon gases hydrocarbon producing Marcellus subgroup at its base (Straeten et al., 2011). The Marcellus at is ~380 ± currently present within shallow aquifers. Herein, we present our initial assessment of the dissolved Figure 5: Variations of [Cl], [Ba], [CH4], and [He] in groundwater and natural salt-rich spring located gas (noble gas and hydrocarbon molecular and isotopic) geochemistry of shallow aquifers in the 15Ma; its age and burial depths were sufficient for the production of mature thermogenic hydrocarbon gases (Engelder and Whitaker, 2006). The UD consists of thick synorogenic deposits including the Brallier, >1km from active shale gas drilling in Pennsylvania and New York. Sample colors indicate the county northeastern tier of Pennsylvania and southeastern tier of New York State. 4 Lock Haven, and Catskill Formations (Figure 3). The latter two formations constitute the two primary where samples were located. CH4 and He concentrations increase with Cl and Ba across the study lithologies that serve as aquifers in northeastern PA, along with the overlying glacial and sedimentary area. The Cl-rich fluids contain elevated Br-/Cl- and Ba/Sr, as well as 87Sr/86Sr consistent with Middle alluvium. Devonian Formation brines (i.e., Marcellus-type) (Warner et al, 2012). Notice that the increase in [CH4] II. Sampling and Methods In the Appalachian plateau physiographic province, the rocks above the Silurian-aged Salina "rolls over" as methane concentrations approach saturation levels for shallow groundwater. The upper formation (including the Marcellus formation) deformed by stably sliding along their basal decollement as limit (solubility saturation = 40 cc/L at 1 atm) for [CH4] demonstrates how groundwater solubility limits We examine the dissolved gas isotopic compositions of 72 domestic groundwater part of the Appalachian plateau detachment sheet (Davis and Engelder, 1985). Deformation within the the maximum dissolved gas concentrations. The positive correlations of [4He] with [Cl], [Ba], and [CH ] wells and one natural methane seep within a seven county area of PA (Bradford, Sullivan, Appalachian plateau detachment sheet is significantly less intense than the Valley and Ridge and is 4 suggests previous migration of a gas-rich, saline fluid from deeper formations into Upper Devonian Susquehanna, and Wayne counties) and NY (Broome, Delaware and Sullivan counties). The accommodated by a combination of layer parallel shortening, folding that lead to the broad 4 study area is within the NAB Plateau region underlain by the Marcellus Shale (~800-2200m anticline/syncline sequences, duplex/thrust faulting structures, and jointing (Lash and Engelder, 2009; aquifers across the region. The coexistence of CH4 and [ He] suggests a thermogenic source of depth) (Figure 2). We integrate our data with previous work on the principal aquifers of the region Scanlin and Engelder, 2003). Each of these deformation features is present and observable within our methane. (Alluvium, Catskill, and Lock Haven) including salt concentrations (i.e., Cl, Ba) and hydrocarbon study area. A combination of thrust-load-induced subsidence, clastic loading, and Alleghanian deformation molecular and isotopic composition (Warner et al., 2012). We place these data within the led to the onset of thermal maturation and eventually catagenesis for the Marcellus Formation. This same geological history of the NAB. This study includes only data from wells located >1km from active hydrocarbon maturation and resulting fluid over-pressuring is suggested as the force that initiated the shale gas development sites including samples targeted for naturally occurring CH4 along with pervasive and systematic joint sets in the Devonian sedimentary sequences throughout the Appalachian plateau (i.e. J and J ) (Engelder et al., 2009; Lash and Engelder, 2009). In our study area, these joint sets other nearby domestic wells in order to characterize geological context of naturally elevated CH4 1 2 V. Noble Gases: Conservative Fingerprint Tracers in the NAB. often cross-cut and are un-mineralized (Lash and Engelder, 2009). All groundwater samples (n=73) were analyzed for their major gas abundance (e.g., 4 21 CH4, C2H6, N2, O2) and noble gas composition (He, Ne, Ar, Kr). The stable carbon isotopic Figure 4: The release of radiogenic isotopes ( He, Ne*, 13 40 composition of methane (δ C-CH4) was determined for all samples with [CH4] exceeding 0.5 cc/L and Ar*) is a function of temperature of the source 2 (n=36), while paired stable hydrogen isotopic composition (δ H-CH4) is available for 30 of the formation (Hunt et al, 2012). As a result, radiogenic samples included in this study. noble gases provide conservative tracers of gas source Before sampling, wells were purged to remove stagnant water and then monitored that are unaffected by microbial activity or subsequent for pH, electrical conductance, and temperature until stable values were obtained. Water samples chemical reactions. Here we show an example of how were collected prior to any treatment systems and were filtered and preserved following USGS paired stable carbon isotopes and radiogenic noble protocols (USGS, 2011). The analysis of inorganic constituents (e.g., Cl, Ba) was reported in gas isotopes can be used to fingerprint the genetic (Warner et al., 2012). Dissolved gas samples were collected for hydrocarbon molecular and source and post-genetic migrational history of stable isotopic composition (e.g., Isotech, 2011; Osborn et al., 2011a). Noble gas samples were Devonian and Ordovician natural gases (Hunt et al, collected in refrigeration-grade copper tubes that were flushed with water prior to sealing with 2012; Darrah et al, 2013). stainless steel clamps (e.g., Dowling et al., 2004). Major gas components (N2, O2, Ar, CH4) were measured using a Dycor quadrupole MS and a SRI GC (e.g., Darrah et al., 2012; Hunt et al., Figure 3): A generalized stratigraphic column (left), areal extent of the Marcellus Formation 2012). The isotopic analyses of noble gases were performed using a VG 5400 MS (e.g., Darrah (right), and a simplified structural cross-section (reproduced from Sak et al, 2012) of the and Poreda, 2012; Poreda and Farley, 1992). northern Appalachian Basin (NAB) plateau in northeastern PA and southeastern NY. The Figure 1: Copper tube sampling method originally Marcellus Formation outcrop belt (upper right) is highlighted in red and the areal extent of devised by Weiss, 1967 is a standard and accepted the Marcellus Formation is shown in purple. The three principal shallow Upper Devonian technique for groundwater gas sampling, specifically dissolved gas components near aquifers include the Catskill, Lock Haven, and surficial alluvium. The generalized structural saturation (e.g., USGS). The sample method cross-section (bottom right) spans from the intensely deformed Valley and Ridge (southeast) VI. CONCLUSIONS: ensures minimal air contamination, accurate to the Appalachian Plateau (to the north and west) across the Appalachian Structural Front assessment of dissolved constituents including (ASF). Samples in this study were collected within the yellow box at distances ranging from •Stray gas investigations should first constrain the geological and hydrogeological helium, hydrocarbons, etc. ~ 20-80km from the ASF. background of a basin targeted for drilling. Figure 2: Digital elevation map of groundwater samples Rifting of the Atlantic ocean, that began in the tertiary and continues today, led to rapid (n=72), sorted by location (county). Shaded brown areas •Stray gas investigations should utilize the full compliment of dissolved gases exhumation/unloading, erosion, and neotectonic jointing (i.e. often termed J3) in at least the top 0.5km of represent higher elevations, while the blue-green demarks the crust (Engelder, 2008). One additional factor that may influence the permeability of aquifers within our •Gas chemistry should be paired with dissolved constituents lower lying areas (valleys). All samples from this study were study area is Pleistocene glacial cycles. Ice loading and retreat led to an additional cycle of shallow crustal collected at distances >1km from active shale gas compaction, glacial isostatic rebound, and likely neotectonic fracturing within NE PA. As a result, previously •Noble gases provide conservative tracers of natural gas: a) source; b) migration; and c) development at the time of sample collection across four deeply buried lithologies such as the Catskill and Lock Haven Formations in our study area are often highly geological history counties in Pennsylvania (Bradford, Susquehanna, Wayne, naturally fractured, dual permeability aquifers today. The majority of stratigraphic sequences above the Sullivan) and 3 counties (Delaware, Sullivan, Broome) in New Catskill Formation are eroded in our study area and therefore not discussed. More complete reviews of York. Previous work identifies increasing [CH ] and salt •Combining noble gas, stable isotopes, and inorganic components allow us to better 4 Carboniferous Age deposition (Mississippian and Pennsylvanian) are available elsewhere (e.g., Faill, concentrations in valley bottoms (Warner et al, 2012, 1997). constrain the geological history of fluid migration in unconventional energy basins Molofsky et al, 2011). (Darrah et al, 2013)